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N',N-双(2-吡啶甲酰胺)-1,2-乙烷稀土配合物与DNA的相互作用的合成及研究

[Synthesis and study on the interaction of rare earth complexes of N', N-bis(2-pyridinecarboxamide)-1, 2-ethane with DNA].

作者信息

Lu Xiao-Hong, Lin Qiu-Yue, Hu Rui-Ding, Liu Wei-Dong, Feng Jie

机构信息

College of Chemical and Life Science, Zhejiang Normal University, Jinhua 321004, China.

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2007 Jun;27(6):1176-80.

PMID:17763786
Abstract

Four rare earth complexes of N', N-bis(2-pyridinecarboxamide)-1, 2-ethane were synthesized and characterized by elemental analysis, conductivity measurement, thermal studies, IR and electronic spectra. The composition of the four complexes is Ln(H2L)(NO3)2 x 3H2O (Ln=Sm, Eu, Gd, Tb). Results of spectral measurements indicate that the oxygen of carbonyl and the nitrogen of pyridyl coordinate with Ln(III) respectively, and the NO3- shows bidentate coordination. So the four complexes are 1 : 1 chelated complexes. The interaction between Sm(H2L) (NO3)2 x 3H2O and DNA was studied by employing UV-Visible (UV-Vis) spectra, fluorescence spectra and SERS spectra. Experimental results show that with the incremental addition of DNA, the bands at 265 nm show hypochromism accompanied by a small red shift and the binding constant Kb Obtained is 1.24 x 10(5). Meanwhile fluorescence spectra show that the addition of [Sm(H2L) (NO3)2] (NO3) x 3H2O to DNA pretreated with EB causes an appreciable reduction in fluorescence intensity, indicating that the complex competes with ethidium bromide in binding to DNA, and free ethidium bromide increases. The addition of DNA causes the SERS signals of the complex to weaken and the band at 1 282 cm(-1) to disappear, which suggests that the planar pyridine molecule of the ligand may partly be inserted into the double-stranded helix plane in DNA, making pi electronic density of aromatic rings in complex change. The above phenomena indicate that [Sm(H2L) (NO3)] (NO3) x 3H2O interacts intensively with DNA.

摘要

合成了四种N', N-双(2-吡啶甲酰胺)-1, 2-乙烷稀土配合物,并通过元素分析、电导率测量、热分析、红外光谱和电子光谱对其进行了表征。这四种配合物的组成是Ln(H₂L)(NO₃)₂·3H₂O(Ln = Sm、Eu、Gd、Tb)。光谱测量结果表明,羰基氧和吡啶氮分别与Ln(III)配位,且NO₃⁻表现为双齿配位。因此这四种配合物是1 : 1螯合配合物。采用紫外可见(UV-Vis)光谱、荧光光谱和表面增强拉曼光谱(SERS)研究了Sm(H₂L)(NO₃)₂·3H₂O与DNA之间的相互作用。实验结果表明,随着DNA的逐步加入,265 nm处的谱带出现减色并伴有小的红移,得到的结合常数Kb为1.24×10⁵。同时荧光光谱表明,向用溴化乙锭(EB)预处理的DNA中加入Sm(H₂L)(NO₃)₂·3H₂O会导致荧光强度明显降低,这表明该配合物与溴化乙锭竞争结合DNA,游离的溴化乙锭增加。DNA的加入导致配合物的SERS信号减弱且1282 cm⁻¹处的谱带消失,这表明配体的平面吡啶分子可能部分插入到DNA的双链螺旋平面中,使配合物中芳香环的π电子密度发生变化。上述现象表明Sm(H₂L)(NO₃)·3H₂O与DNA有强烈的相互作用。

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